Phosphate dentifrice



tics of these formulations;

. tor the dicalcium dehydrated on aging, thcrb causing the paste to become formulations. However,

which include such .gurns the addition of about 0.6%

phoric acid modified dicalcium United States Patent Ofi ice 3,169,096 PHQSPHATE DENTEFRICE Julian R. Schlaeger, Chicago Heights, and Lowell E.

Netherton, Park Forest, liL, assignors to Stanfiel- Chemical Company, New York, N.Y a corporation of Delaware No Drawing. Original application .i'nne 30, 1959, Ser. No. 823,822, now Patent No. 3,066,056, dated Nov. 27,

1962. Divided and this application Jan. 15, 1962, Ser- No. 166,394 p v 2 Claims. '(Cl. 167-93) This invention relates to stabilized dicalcium phosphate dihydrate compositions containing controlled proportions of in-situ formed calcium pyrophosphate and added sodium-calcium pyrophosphate, dentifrice compositions containing said stabilized dicalcium phosphate dihydrate compositions, and methods of producing same.

This application is a division of our prior copending' application, Serial No. 823,822, filed on'June 30, l 95 9 now US. Patent 3,066,056.

Dicalcium phosphate dihydrate is a highly desirable abrasive component for use in dentifrice formulations because of its mild abrasive characteristics With respect to tooth enamel. However, because of its instability against dehydration, it is not entirely satisfactory for use in manydentifrice compositions. Partial or complete dehydration of the dicalcium phosphate dihydrate in either powdered or paste :type dentifrice formulations results in undesirable variations in the abrasion and other physical characteris For example, when uscdin u dentifrice paste formulations containingwater and. a

humectant such as glycerine or sorbitol, there is tendency phosphate dihydrate to become partially gritty or stiffen, or even set Considerable eifort has been made in the past to stabil ze to form a hard non-extrudable desiccator for one to two hours atroom theddicalcium phosphate dihydrate for use in dentifrice limited success, particularly, in its use inpaste type formulations .suchas the currently. popular paste formulations additives (cg. sarcosinates, ,etc.) which providethese formulations with increased hygienic properties.

. We have now found that the above difiiculties maybe 7 7 substantially overcome by-the combined use of controlled levels of in situ formed calcium pyrophosphate and finely theseefforts have met with onlyas carboxymethyl cellulose and i p strength. To this solution, 4.0

,sti'rring" at a rate sufiicient to H temperature Within the range of about to C. The

3,169,096 Patented Feb. 9, 1965 and mechanically added calcium-sodium pyrophosphate.

in the same proportions that control the stability of the dicalcium phosphate dihydrate against dehydration. EX- ample, Vl, infra, illustrates the procedure that may be used for producing our stabilized dicalcium. phosphate dihydrate.

Determinations of stabilityof the dihydrateagainst hydration may be calcium phosphate modified) .-in a 2 /2 made by placing 1'0 grarnsof the di dihydrate product (modifiedor uninch diameter moisture pan and holding the pan in a humidor in an atmosphere of 75% relaat a temperature of about 60 C. for

tive humidity and 7 periods rangingafrom one to thirteen days. The amount of dehydration may beobtained by determining the loss onignition after drying in a calcium chloride containing temperature. 'By comparison with an original sample, the difference in loss may be calculated as percent conversion to the anhydrous salt. 1 The stability data ofExamples I -II I,- infra, were obtained in this manner.

CEXAVMPLE I In order to prepare dicalcium phosphate dihydrate, a welghed quantity of orthophosphoric acid may be diluted I i with sufiicient Water to adjustthe solution to about '15 a milk of limeslurry of may be added with rapid maintain thecharge at aabout 8? :to 10 B.. strength --addition of milk of lime should be continued so as to divided calcium-sodium pyrophosphate additives in. conjunction' with dicalcium phosphate dihydrate. This com bination of additives renders the .dicalcium phosphate dihydrate stable against-dehydration under nprmalstorage conditions, gives it th'eability to provide a suitable viscosity to toothpastes employing various humectants and stabilizes paste type (e.g., glycerine and/ or sorbitol), dentifrice formulations containing dicalcium 7 phosphate changes in viscosity and gel strength).

It'has been found that control of these characteristics may be effected by the introduction of fromabout 0.4%

(or at least 0.'l '6%-f-H P O-i) .to about 0.8% by Weight (based; on the Weightof. the final stabilized dihydrate) of pyropho'sphorica cid (at;leas't 40% H P O' in the process of manufacturing the 'dicalciurn phosphate dihydrate plus to about 1.2% by weight (based on the; weight of the final stabilizeddihydrate) ofpreviously prepared, 'finelydivided "sodium-calcium dihydrate against changes which occuriupon aging (e.g.,j

pyrophosp'hate" to the finished,- finely :divided, pyrophostals. Bothadditio'ns are essential to our invention since neither of these treatments alone produce a dicalcium phosphate dihydrate composition having the above desiredj characteristics.

phosphate dihydratecrys complete the neutralization and precipitation of dicalciuml phosphate dihydrate crystals and produce a'mother liquor having apH of about 7.

I The dicalciumphosphate dihydrate product mayfthen produce a product having particles smaller than about 40 microns in diameter. 1 '3 One percent by weight of finely divided. sodium-calcium ,pyrophosphate (CaNa 'P O -4H O should be mechani'cally mixed with dicalcium phosphate dihydrate that was 7 produced in accordance with the above-described pro-,

cedure. This product"isunstable bccause about 66% by weight of the dicalcium. phosphate, dihydrate iconverted toanhydrous dicalciumphosphate uponflstorage for one dayaa't 60 humidity.

C. in an atmosphere of about relative As pointed -outin Example I above, dicalcium phosphate dihydrate may, be prepared by first diluting a weighed quantity of orthophosphoric acid with sufficient B. strength. To

water to adjust the solution to about 15 this solution a milk of lime slurry of about 10 B. strength maybe added with'rapid stirring at a rate suflicient to maintainthe charge at a. temperature within the range of 35 to 45 f C. The reaction maybe permitted to continue until the pHl v alue of the liquor is aboutS-GQ At this point,.' 0.4%Qbyfweight pyrophosphoric facid should be added'to 'the'lreaction mixture. The additionof the milk .oflime should be continued to complete the neutralizabe filtered out anddried to.

tion and precipitation of the dicalcium phosphate dihydrate crystals and produce a mother liquor having a pH of about 7. The pyrophosphoric acid modified dicalcium phosphate dihydrate may then be filtered out and dried to produce a product having particles smaller than about 40 microns in diameter. The product is un stable as evidenced by the conversion of the 44% by weight of the dicalcium phosphate dihydrate to anhydrous dicalcium phosphate upon storage for six days at the test conditions set forth in Example I, supra.

EXAMPLE 111 On the other hand, when the same levels of sodiumcalcium pyrophosphate and pyrophosphoric acid of Examples I and II, respectively, are both added in'accordance with the procedures set forth in these examples, the resulting product is significantly more stable than the ,products produced by Examples 1 and II. 'Only by weightof the dicalcium phosphate dihydrate converted to the anyhydrous form upon storage for ten days at the i test conditions set forth in Example-I, supra.-

- Example IV, infra, shows that the product of Example III, supra, in glycerin-water solutions, is superior to the products of Examples l and II, supra.

EXAMPLE v Stability determinations of thedicalcium phosphate dihydrate in glycerin-water solutions were made by placing 25 grams otthe dicalcium phosphate dihydrate sample in a 100 ml. glass beaker and adding increments of an 80%.

to 20%. glycerin-Water solution, with stirring, until a thin paste was formed. The consistency of the paste was de termined by drawing a glass rod across the surface, t.he'reby making a track which disappeared within a fewsecends. The paste was then pouredinto a Pyrex test tube and suspended in'boilingwater (i'.e., 100 C.) for'30 minutes. The slurry was then thinned with methanol and filtered, and further washed with methanol to remove all glycerin from the dicalciurn phosphate residue. residue was allowed to dry at room temperature. The

. loss on ignition was then determined. By comparingthis' loss with the originalsample, the difierence in loss is calculated as percent conversion to the anyhdrousforms Sixty-four percent by weightof the dicalciumphosphate dihydrate .(this of course excludes the additives) converted-t0 the anhydrous formywhen the product of Example I, supra, was added to the glycerin-water solution for /2 hour at 100 C.

1 Fifty-two percent by weight of the dihydrate converted to the anyhdrous form when the product of Example 11, supra, was added to the glycerinwatersolution for /2 hour at 100 C.

Only 13 by weight of the dicalcium drate converted to the anyhdrous. form phosphate dihysolution for /2 hour at' 100 C. v T Example V, infra, shows that dicalcium phosphate d1= The dicalcium phosphate when the product ofExarnple III, suprapwas added to the glycerin-water;

cium-sodium pyrophosphate in proportions which are within the range suitable for controlling the stability of the dicalcium phosphate dihydrate against dehydration.

EXAMPLE V In order to illustrate the effect of our combination of additives upon the viscosity of toothpastes containing dicalcium phosphate dihydrate, sorbitol and carboxymethyl cellulose, viscosity studies were made with Formulation A, infra.

The viscosity measurements were made'using a Brookfield Synchro-Lectric Viscometer (Multi-Speed Model HAF). Each reported measurement represents the average of five separate measurements. The viscosity readings were converted to centipoises to give'the values reported.

It was found that the viscosities of pastes of the above I type may be essentially controlled by controlling the proportions of the calcium-sodium pyrophosphate and pyrophosphoric acid employed; For example, the inclusion of 0.4% by weight in-process added pyrophosphoric acid and 0.6%, 1.0% and 1.2% by Weight mechanically mixed incalcium-so'di'um pyrophosphatdin the dicalcium phosphate dihydrate constituent of Formulation A caused Formulation A to have viscosity'values of 260,000, 480,-

000, 'and 700,000 centipoises, respectively, after aging for ten days. Whenthe dicalciurn phosphate dihydrate j constituent of Formulation A contained mechanically mixed incalcium-sodium pyrop-hosphate, and no pyrophosphoric acid, in amounts of 0.6%to 142% by weight, the formulation had viscosity values ranging from 100,000v

hydrate containing'either in-process added pyrophosphoric acid or mechanically added calcium-sodium pyrophosphate results, inincreasing 'the viscosity of the toothpastes used as the level of the; additives. in thedicalcium phosphate dihydrate the in-process phosphateadditive has a modifying eltect ontherate of the increase of viscosity when used in amountsof up to about 1.25%by weight of the dicalciurn phosphate di-' hydrate employed in the paste.v Thus, the modifying effect of the calcium sodiu'm pyrophosphate additive is much less pronounced in'pastes'in thehigher visco's ity range, namely, in the order of. 700,000 centipoises or higher. Example V'thus demonstrates the control. of

toothpaste viscosity overa wide range .with dicalciurn.

phosphate dihydrate compositions containing in-process added pyrophosphoric acid' and mechanigally added calcomponent increases, with the efiect oi added-pyrdphosphoricacid causing the morerapid rise inviscosity. The calcium-sodiumpyrotoonly 370,000 'centipoises after fourteen days; Our stabilized dicalcium phosphate-dihydrate product also improves toothpastes formulated with humectants such'as glycerineand, mixtures of glycerine and sorbitol.

Formulation B illustrates an example of this type of formulation:

i y )0 Paste Formulation B p Y Percent-by weight D calciurn phosphate dihydrate constituent (i.e.,

modified or unmodified constituent) 50.0 Glycerin ;Q 4.0 Sotbitol 20.0 Irishmoss (as gum) 1.0 '-Water Sodium lauryl sulfate i I 1.8 SaccharinV; L 0.1

It was found that with pastes as :Forrnulation B, the

use ofdicalcium phosphate dihydrate constituents con- 7 v taining 0.4%, 05%, and 1.25% by weight, respectively,

of i i-process added pyrophosphoric acid, caused the resulting pastes to haveviscosity values of 236,000, 310,000, and 850,000 (a stiff. paste) centip'oises a'fter'v aging for fourteen. days.

- vStill further, our additives improve'toothpaste formu- I lations of 'the'typeshown in Formulation B, supra, where- 'in' about 7% sorbitol and about2l% glycerin are used.

Whenthe dicalcium phosphate dihydrate constituent in this type of formulation 'contains' 1.25% by weight inprocess added pyropho s'phoric acid and 0.6% mechanivcally mixed in calcium-sodium pyrophosphate, the paste has a viscosity of about 500,000 centipoi'ses after fourteen days, as compared with about 249,000 centipoises which is obtained when the dihydrate constituent includes 0.4% by weight in-process added pyrophosphoric acid and 0.9% by weight calciumesodium pyrophosphate.

Under accelerated test conditions, increasing the amount of in-process added pyrophosphoric acid to 0.8% by weight of the dicalcium phosphate dihydrate produces a stabilized product; a product in which only 3% by weight of the dicalcium phosphate dihydrate is converted to the anhydrous form on storage for ten days at 60 C. in an atmosphere of 75% relative humidity, using the test procedure set forth above with respect to Examples I-III. No further increase in the stability was'eifected by the addition of 1.2% by weight of calcium-sodium pyrophosphate to the 0.8% by weight pyrophosphoric acid modified product. Larger amounts of the two additives do not further improve appreciably the stability of the dicalcium phosphate dihydrate against dehydration under equivalent test conditions. Thus, the upper limit for the synergistic effect of the two additives upon the stability of the dicalcium phosphate dihydrate against dehydration is about 0.8% by weight in-process added pyrophosphoricacid and about 1.2% by weight mechanically mixed in calcium-sodium pyrophosphate. With lower amounts of the in-process added pyrophosphoric acid, stability decreases rapidly. For practical purposes, the use of about 0.4% by weight in-process addedpyrophosphoric acid and about 0.6% by weight mechanically added calciumsodium pyrophosphate represents the minimum desired levels of the two additives for commercial purposes.

An example of the method of preparing our new stabilized dicalcium phosphate dihydrate composition may" be illustrated as follows: 1

EXAMPLE VI A weighed quantity of orthophosphoric acid was diluted with sutlicient water to adjust the solution to about CaNa P O filtered, washed, and dried. If necessary, the product may be milled to a particle size of less than 40 microns.

In the reaction for the production of the dicalcium phosphate dihydrate, the in-process added pyrophosphoric acid should be neutralized by the final addition of milk of lime. Calculations indicate thatwhen 0.4%'by weight pyrophosphoric acid containing 40% H P O (by chromatographic analysis) is added to the reaction mixture, the (321 1 0 content of the final product should be about 0.23% by weight. On the other'hand, when 0.8% by weight pyrophosphoric acid containing 50% H P O (by chromatographic analysis) is used, the resulting product should contain about 0.57% Ca P O For purposes of the present invention and the following claims, the minimum level of H P O used is intended to be 0.16% by weight based on the dihydrate, which results when 0.4%

15 B. strength. To this solution, a milk of limeslurry of about 8 to 10 B. strength was added with rapid stirring at a rate sufficient to maintain the charge at a V 7 temperature within the range of 35 to b C. The course i of the reaction was permitted to continue until the pH value of the charge liquor was, within the range of 5.0 to 6.5 (a pH of 6 is preferred); At this point,.from 0.4% to 0.8 by weight of pyrophosphoric acid (40% to by weight H l o contentfbased on the weight of the calculated stoichiometric quantity of dicalcium phosphate dihydrate equivalent of the phosphoric acid in the charge was added. The addition of the milk of lime was then continued to complete the neutralization and precipita- 'iritimately bonded product that results when pyrophosphoric .acid is added to the dicalcium phosphate dihydrate reaction mixture prior to its complete neutralization and prior to the completion of the formation of the dihydrate crystals.

The percentages of pyrophosphoric acid and sodiumcalcium pyrophosphate are herein based on the final or total weight of the stabilized dihydrate product (includes the dihydrate 'plus these additives). I

The foregoing detailed description has been given for clearness of understanding only, and no unnecessary limitations should be understood therefrom, as modifications will be obvious to those skilled in the art.

We claim: t Y a V 1. A dentifrice paste composition comprising: water;

humectant; and a stabilized dicalcium phosphate dihytion ofthe dicalcium phosphate dihydrate crystals from a mother liquor having a pH value of about 6.9 to 7.2 (preferably about 7.1). The pyrophosphoric acid modified dicalcium phosphate dihydrate product was filtered out and dried. The product may be milled to produce a product substantially all of which has a smaller than 40 microns in diameter.

From 0.6% to 1.2% by weight of a substantiallywaterinsoluble, finely divided calcium-sodium pyrophosphate particle size (CaNa P O -4H O) was added and the materialsithofi oughly mixed to effect a homogenous distribution of the sodium-calcium pyrophosphate throughout the dicalcium phosphate dihydrate product. pH within the range of 7.0 to 7.7.

I It is not known in what form the added pyrophosphoric The final product had a acid appears in the final product, but presumablythe acid .is'neutralized to calcium pyrophosphate in the final stages of the manufacturing procedure with the calcium pyro-- phosphate being-coprecipitated or adsorbed 'on the surfaces of the dicalcium phosphate dihydrate crystals. It is important that the pyrophosphoric acid be added prior to the final neutralization with lime.

The term pyrophosporic acid is intended to include mixtures of polyphosphoric acids containing at least 40% drate; said stabilized dicalcium phosphate dihydrate being produced by a method which comprises first reacting a. dilute solution of orthophosphoric acid with milk of lime t oproduce a reaction mixturehaving a pH between about 5 and the neutralization point, then addingabout 04-08% by weight of a polyphosphoric'acid having at least40% by weight pyrophosphoric acid,-then completing the neutralization of the reaction mixture with the ad dition of'milk-oflime until a pH of about 6.9-7.2 is

reached, removing and drying the dicalcium phosphate dihydrate formed from the reaction mixture, then ad- .mixing an effective, stabilizing amount of finely divided calcium-sodium pyrophosphate with the pyrophosphoric acid-modified dicalcium phosphate dihydrate to produce phosphate dihydrate product,

said stabilized dicalcium and recovering a stabilized improved dicalcium phosphate dihydrate product. 7 V

. 2.- A stable dentifrice composition comprising: stabilized dicalcium phosphate dihydrate produced by a method which comprises first reacting a dilute solution of orthophosphoric acid with milk of lime to produce a reaction mixture having a pH of about 56.5, then adding about 0.400.8% by weight of a polyphosphoric acid having at least 40% by weight pyrophosphoric acid,

then completing the neutralization of the reaction mixture with the addition of milk of lime until a pH of about 6.9-7.2 is reached, removing and drying the dicalcium pyrophosphoric acid contains 40%' phosphate dihydrate formed from the reaction mixture, then admixing about 0.61.2% by weight of finely divided calcium-sodium pyrophosphate With'the pyrophosphoric acid-modified dicaleium phosphate d'ihydrate to produce said stabilized dicalcium phosphate dihydrate product, and recovering a stabilized improved dicalcium phosphate dihydrate product; Water; and humectant from the group consisting of glycer inand sorbitol.

References Cited by the Examiner UNITED STATES PATENTS 2,287,699 6/42 Moss et a1. 167-93 5 LEWIS GOTTS, Primary Examiner;

M. O. WOLK, IRVING MARCUS, Examiners. 

2. A STABLE DENTIFRICE COMPOSITION COMPRISING: STABILIZED DICALCIUM PHOSPHATE DIHYDRATE PRODUCED BY A METHOD WHICH COMPRISES FIRST REACTING A DILUTE SOLUTION OF ORTHOPHOSPHORIC ACID WITH MILK AF LIME TO PRODUCE A REACTION MIXTURE HAVING A PH OF ABOUT 5-6.5, THEN ADDING ABOUT 0.40-0.8% BY WEIGHT OF A POLYPHOSPHORIC ACID HAVING AT LEAST 40% BY WEIGHT PYROPHOSPHORIC ACID, THEN COMPLETING THE NEUTRALIZATION OF THE REACTION MIXTURE WITH THE ADDITION OF MILK OF LIME UNTIL A PH OF ABOUT 6.9-7.2 IS REACHED, REMOVING AND DRYING THE DICALCIUM PHOSPHATE DIHYDRATE FORMED FROM THE REACTION MIXTURE, THEN ADMIXING ABOUT 0.6-1.2% BY WEIGHT OF FINELY DIVIDED CALCIUM-SODIUM PYROPHOSPHATE WITH THE PYROPHOSPHORIC ACID-MODIFIED DICALCIUM PHOSPHATE DIHYDRATE TO PRODUCE SAID STABILIZED DICALCIUM PHOSPHATE DIHYDRATE PRODUCT, AND RECOVERING A STABILIZED IMPROVED DICALCIUM PHOSPHATE DIHYDRATE PRODUCT; WATER; AND HUMECTANT FROM THE GROUP CONSISTING OF GLYCERIN AND SORBITOL. 